US5338571A - Method of forming self-assembled, mono- and multi-layer fullerene film and coated substrates produced thereby - Google Patents

Method of forming self-assembled, mono- and multi-layer fullerene film and coated substrates produced thereby Download PDF

Info

Publication number
US5338571A
US5338571A US08/016,820 US1682093A US5338571A US 5338571 A US5338571 A US 5338571A US 1682093 A US1682093 A US 1682093A US 5338571 A US5338571 A US 5338571A
Authority
US
United States
Prior art keywords
fullerenes
solution
bond
substrate surface
chemically modified
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US08/016,820
Inventor
Chad A. Mirkin
Kaimin Chen
W. Brett Caldwell
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northwestern University
Original Assignee
Northwestern University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Northwestern University filed Critical Northwestern University
Priority to US08/016,820 priority Critical patent/US5338571A/en
Assigned to NORTHWESTERN UNIVERSITY reassignment NORTHWESTERN UNIVERSITY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: CALDWELL, W. BRETT, CHEN, KAIMIN, MIRKIN, CHAD A.
Application granted granted Critical
Publication of US5338571A publication Critical patent/US5338571A/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • B05D1/185—Processes for applying liquids or other fluent materials performed by dipping applying monomolecular layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/84—Manufacture, treatment, or detection of nanostructure
    • Y10S977/842—Manufacture, treatment, or detection of nanostructure for carbon nanotubes or fullerenes

Definitions

  • the present invention relates to the formation (self-assembly) of covalently bound mono- and multilayered fullerene films or layers on insulating, semiconducting, and metallic substrates.
  • Physisorbed, multilayer films of the fullerene C 60 have exhibited interesting mechanical, electrical, electrochemical, and optical properties.
  • Such physisorbed fullerene films have been formed on substrates by the well known Langmuir-Blodgett (LB) technique and by the solution evaporation technique using C 60 solutions (e.g. C 60 dissolved in non-polar organic solvents such as benzene, toluene, etc.).
  • C 60 solutions e.g. C 60 dissolved in non-polar organic solvents such as benzene, toluene, etc.
  • Such physisorbed films also have been formed by thermal evaporation of solid phase fullerenes onto a suitable substrate.
  • a method for forming a fullerene layer on a substrate by chemically treating a surface of the substrate to provide a bond-forming species at the surface effective to covalently bond with fullerenes in solution and contacting the treated substrate surface with a solution of fullerenes to form a fullerene layer covalently bonded to the treated substrate surface.
  • the substrate surface can be treated to provide a bond-forming species that forms carbon-nitrogen bonds with fullerenes in solution.
  • the substrate surface can be treated prior to contacting the solution of fullerenes to provide amine bond-forming species or sites at the treated substrate surface.
  • the substrate surface can be treated to provide a bond-forming species that forms a carbon-carbon bond with fullerenes in solution.
  • the substrate surface can be treated prior to contacting the solution of fullerenes to provide alkyl anion species at the treated substrate surface.
  • the substrate surface can be treated to provide a bond-forming species that forms a carbon-oxygen bond with fullerenes in solution.
  • the substrate surface can be treated prior to contacting the solution of fullerenes to provide transition metal oxide species at the treated substrate surface.
  • the fullerenes can be dissolved in a nonpolar organic solvent that is contacted with the treated substrate surface to form the fullerene layer covalently bonded to the treated substrate.
  • a three dimensional multilayer fullerene structure can be formed on the substrate surface by chemically modifying an initial fullerene layer formed thereon in the manner described above to provide chemical bridging species (e.g. piperazine) covalently bonded thereto and effective to covalently bond with fullerenes in solution.
  • the modified fullerene film then is contacted with a solution of fullerenes to form a second fullerene layer covalently bonded to the initial fullerene layer by the chemical bridging species.
  • the method can be repeated to build up additional fullerene layers on the substrate surface.
  • a method for forming a fullerene layer on a substrate by chemically modifying fullerenes to provide a bond-forming species thereon, chemically treating a surface of the substrate to provide a bond-forming species effective to covalently bond with the bond-forming species of the fullerenes in solution, and contacting a solution of modified fullerenes with the treated substrate surface to form a fullerene layer covalently bonded to the treated substrate surface.
  • fullerenes in solution are treated to form hydrosilated fullerenes and the substrate surface is treated to provide hydroxy groups that covalently bond with the hydrosilated fullerenes in solution.
  • the hydrosilated fullerenes can be dissolved in a nonpolar organic solvent that is contacted with a base treated substrate surface to form the fullerene layer covalently bonded to the treated substrate.
  • a three dimensional multilayer fullerene structure can be formed on the substrate surface by chemically modifying an initial fullerene layer formed thereon in the manner described above to provide chemical bridging species (e.g. piperazine) covalently bonded thereto and effective to covalently bond with modified or unmodified fullerenes in solution and contacting the modified fullerene film with a suitable fullerene solution to form a second fullerene layer covalently bonded to the initial fullerene layer by the chemical bridging species.
  • chemical bridging species e.g. piperazine
  • the present invention provides in accordance with still another aspect of the invention a fullerene coated substrate having a surface treated to covalently bond with fullerene molecules and a fullerene layer covalently bonded to the treated substrate surface.
  • the fullerene layer can be covalently bonded to the treated substrate surface by carbon-nitrogen, carbon-carbon, carbon-oxygen, and/or carbon-silicon covalent bonds. Additional fullerene layers can be covalently bonded to the fullerene layer by chemical bridging species to form multilayer fullerene structures.
  • the present invention also provides novel layers of fullerenes.
  • FIG. 1A is a cyclic voltammogram for a self assembled C 60 monolayer on (MeO) 3 Si(CH 2 ) 3 NH 2 -treated indium-tin oxide (ITO) electrode (0.5 cm 2 ) in CH 2 Cl 2 /0.1M Bu 4 NPF 6 .
  • FIG. 1B is a cyclic voltammogram for a self-assembled C 60 monolayer on (MeO) 3 Si (CH 2 ) 3 NH 2 -treated indium-tin oxide (ITO) electrode (0.8 cm 2 ) in CH 2 Cl 2 /0.1M Bu 4 NPF 6 after refluxing in a 5 mM benzene solution of para-ferrocenylaniline for 2 days.
  • ITO indium-tin oxide
  • FIG. 1C illustrates a synthesis procedure for self-assembling C 60 on an amine-modified oxide substrate surface through carbon-nitrogen bond formation.
  • FIG. 2A illustrates another synthesis procedure for self assembling C 60 on a cysteamine/ethanethiol-modified Au substrate surface through carbon-nitrogen bond formation.
  • FIGS. 2B and 2C are a cyclic voltammograms for a self assembled C 60 monolayer on cysteamine/ethanethiol-treated and cysteamine-2-mercaptoethanol treated Au electrodes (0.34 cm 2 and 0.56 cm 2 ) in CH 2 Cl 2 /0.1M Bu 4 NPF 6 .
  • FIG. 3 illustrates a synthesis procedure for self-assembling C 60 on a chloropropylthiol-modified metal substrate surface through carbon-carbon bond formation.
  • FIG. 4 illustrates a synthesis procedure for self-assembling C 60 on a transition metal oxide-modified metal substrate surface through carbon-oxygen bond formation.
  • FIG. 5A illustrates a synthesis procedure for self assembling modified C 60 /C 70 fullerenes on a base-treated substrate surface through carbon-silicon bond formation.
  • FIGS. 5B, 5C, and 5D are cyclic voltammograms for hydrosilated C 60 in solution (FIG. 5B), hydrosilated C 60 /C 70 in solution (FIG. 5C), and a self-assembled hydrosilated C 60 monolayer (FIG. 5D) on base-treated indium-tin oxide (ITO) electrode (0.25 cm 2 ) in CH 2 Cl 2 /0.1M Bu 4 PF 6 .
  • ITO indium-tin oxide
  • a method for forming a fullerene monolayer on a substrate by chemically treating a surface of the substrate to provide a bond-forming species at the surface effective to covalently bond with fullerenes in solution.
  • fullerene as used herein is intended to include C 60 , C 70 , and other solely carbon molecules classified in the fullerene family of molecules.
  • the substrate surface can be treated to provide a bond-forming species that forms covalent bonds with fullerenes in solution.
  • ITO substrate indium-tin oxide (ITO) substrate is treated to provide an amine bond-forming chemical species thereon.
  • a base-treated (treated in 0.5M KOH ethanol/water solution for 3 hours at room temperature) ITO substrate is soaked in a 0.25M benzene solution of (MeO) 3 Si(CH 2 ) 3 NH 2 under reflux conditions for 8-12 hours. The substrate then is removed and rinsed with benzene, dichloromethane, and acetonitrile in sequence. The decreased hydrophilicity of the treated surface is verified with contact angle measurements (theta 46 degrees) as set forth in Table I below. Such contact angle measurements are commonly used to assess surface composition. A Rame-hart Model A-100 Goniometer was used for all contact angle measurements.
  • the (MeO) 3 Si(CH 2 ) 3 NH 2 -treated substrate then is soaked in a 1 mM benzene solution of C 60 for 1-2 days under reflux conditions.
  • the C 60 dissolved in the benzene solution was obtained by the carbon arc method wherein a 1 inch diameter by 6 inches long graphite rod is arced in a water cooled vacuum arc furnace using about 10% of a 120 KW (400Amp at 300 volts DC) power source.
  • the 1 inch diameter by 6 inches long graphite is converted to soot in 15 minutes using this procedure.
  • the C 60 and C 70 fullerenes are separated from the soot chromatographically using a SOXHLET extractor with an alumina packed column.
  • the substrate After soaking in the C 60 solution for 1-2 days, the substrate is rinsed and sonicated in benzene for 2 minutes to remove residual physisorbed C 60 and then further rinsed with dichloromethane and tetrahydrofuran (THF).
  • THF dichloromethane and tetrahydrofuran
  • Quartz and glass substrate surfaces can be coated with C 60 in a similar manner as described for the ITO substrate surface.
  • the resolution of the waves of FIG. 1A reflect the homogeneity of the surface fullerene species and suggests that each fullerene in the layer has a similar chemical identity, mono- and/or di-substituted adducts. Assuming each wave in FIG. 1A corresponds to a one electron transfer, integration of the current associated with the waves is consistent with monolayer coverage of the substrate surface (e.g. approximately 1.7 ⁇ 10-10 mol/cm 2 ). Models based on crystallographic data for C 60 predict a surface coverage of approximately 1.9 ⁇ 10 -10 mol/cm 2 for a closed packed monolayer of C 60 .
  • the C 60 layer formed in the manner described above can be chemically modified by reaction with a variety of amine reagents to build up multilayer C 60 film structures.
  • the steps shown can be repeated to build up a multilayer C 60 structure wherein C 60 layers are covalently bonded via piperazine bridging species (providing covalent carbon-nitrogen bonds) in the manner shown in FIG. 1C.
  • the number of C 60 layers formed on the substrate surface can be controlled by the number of times that the steps of FIG. 1C are repeated.
  • the C 60 layer formed in the manner described above can be modified by reaction with amine reagents shown in Table I above.
  • amine reagents shown in Table I above There is excellent correlation with the type of amine reacted with the C 60 layer and the expected wettability of the surface obtained from such a reaction.
  • ethylmethylamine reacted with the C 60 layer yields a surface with a contact angle of 63 degrees
  • the surface coverage of the para-ferrocenyl aniline layer is 1.2 ⁇ 10 -10 mol/cm 2 as determined by integration of the current assigned to ferrocene oxidation, FIG. 1B.
  • the E 1/2 value for the adsorbed para-ferrocenylaniline is 0.10 V more positive than the E 1/2 for para-ferrocylaniline in solution (-0.06V vs. Fc/Fc+). This shows that the NH 2 of para-ferrocenylaniline has reacted with C 60 and the shift in E 1/2 to more positive values reflects the electron withdrawing nature of C 60 .
  • the para-ferrocenylaniline-C 60 bilayer films are indefinitely stable to cycling through ferrocene oxidation, but these bi-layer films lose electrochemical activity when held at negative potentials (-1.8V) for extended periods of time.
  • X-ray photoelectron spectroscopy (XPS) before and after electrochemical cycling of these bi-layer films confirm removal of the ferrocenylaniline and C 60 layers from the substrate (electrode) surface. This is done by comparing the XPS lines of (Cls), N(ls), and Fe(2p) before and after electrochemical removal of fullerenes from the surface. This demonstrates the ability of the invention to adsorb/desorb a portion or all of the fullerene monolayer (i.e. to alter the amount of fullerine present on the substrate) by applying negative potentials to the coated substrate.
  • the surface of a gold (Au) substrate is treated to provide a preadsorbed monolayer of NH 2 CH 2 CH 2 SH (cysteamine) as depicted in FIG. 2A.
  • a Au substrate electrowette
  • a Au substrate is soaked in a 1.0 mM solution of HS(CH 2 ) 2 NH 2 for 24 hours.
  • the resulting substrate is repeatedly rinsed in ethanol, CH 2 Cl 2 and benzene in sequence.
  • the increased hydrophobicity of the resulting substrate surface is confirmed via contact angle measurements, Table II.
  • the cysteamine-treated Au substrate then is soaked in a 1 mM toluene solution of C 60 for 24 hours at room temperature.
  • the resulting substrate is rinsed in benzene and CH 2 Cl 2 to remove physisorbed C 60 .
  • the increased hydrophobicity of the resulting treated surface is confirmed via contact angle measurements.
  • the electrochemistry of the C 60 coated Au substrate surface exhibits broad features consistent with a somewhat passivated electrode surface. This is in contrast to monolayers of C 60 formed in the previous Example 1, which exhibit two distinctive electrochemically reversible reductive waves under similar electrochemical conditions.
  • the broad features appear to be due to the resistance associated with the incorporation of charge compensating ions into the hydrophobic C 60 monolayer film.
  • each wave in FIG. 2B corresponds to a one electron transfer
  • integration of the current associated with the waves is consistent with monolayer coverage of the substrate surface (e.g. approximately 1.7 ⁇ 10 -10 mol/cm 2 ).
  • a prelayer formed from a solution of 2-mercaptoethanol:cysteamine can also be used to this end.
  • mixed solutions are prepared in different molar ratios of 2-mercaptoethanol and cysteamine.
  • Gold substrates are immersed in these ethanol solutions at room temperature for 24 hours.
  • the substrates are rinsed with ethanol, THF, dichloromethane, and benzene and then immersed in 1 mM benzene solutions of C 60 for 24 hours.
  • the substrate is rinsed in benzene, THF, and dichloromethane to remove physisorbed C 60 .
  • FIG. 2C shows the cyclic voltammogram obtained from a substrate immersed in a 20:1 molar ratio solution of mercaptoethanol to cysteamine. Two reversible waves are observed at -1.19 and -1.55V vs.
  • the prelayer can comprise bond-forming species and diluant species (e.g. ethanethiol 2-mercaptoethanol, etc., present in a selected amount to control the amount of fullerene formed on the prelayer upon contact with a solution of fullerenes.
  • bond-forming species and diluant species e.g. ethanethiol 2-mercaptoethanol, etc.
  • the surface of a Au substrate is treated to provide an alkyl anion bond-forming chemical species thereon as shown in FIG. 3 to form a carbon-carbon bond between the fullerenes and the treated substrate.
  • an Au electrode is soaked in a 2 mM ethanol solution of chloropropylthiol overnight at ambient temperature.
  • the treated substrate surface is rinsed with ethanol and tetrahydrofuran.
  • the treated substrate surface is then soaked in a 5 mM tetrahydrofuran solution of sodium naphthalide (or lithium naphthalide) at -38 degrees C. for 1 hour under a nitrogen atmosphere.
  • the substrate After rinsing with tetrahydrofuran and benzene in sequence, the substrate is soaked in a 1 mM benzene solution of C 60 for 2 hours at ambient temperature in a nitrogen atmosphere.
  • the C 60 coated Au substrate is rinsed vigorously with benzene and tetrahydrofuran in sequence.
  • the anionic self-assembled monolayers of C 60 can be quenched with a variety of reagents, such as CH 3 CH 2 OH, H 2 O, CH 3 I, (CH 3 ) 3 OBF 4 , and CF 3 SO 3 CH 3 to form neutral C 60 monolayers.
  • reagents such as CH 3 CH 2 OH, H 2 O, CH 3 I, (CH 3 ) 3 OBF 4 , and CF 3 SO 3 CH 3 to form neutral C 60 monolayers.
  • These C 60 monolayer films also has been characterized by XPS (XPS lines S(2p), Cl(2p), and C(1s) are compared before and after C 60 self-assembly).
  • the surface of a Au (or Pt) substrate is treated to provide transition metal oxide bond-forming species in the manner illustrated in FIG. 4 and described below.
  • a Au substrate is exposed to a 5 mM solution of 4-mercaptopyridine in absolute ethanol for 24 hours.
  • This treated substrate is removed and rinsed with ethanol, benzene, and dichloromethane in sequence.
  • the substrate then is placed in a 1 mM solution of osmium tetroxide in toluene in a dry box for 24 hours.
  • the treated substrate is removed and rinsed with toluene, tetrahydrofuran and dichloromethane in sequence.
  • the substrate is exposed to a 1 mM solution of C 60 in toluene for 24 hours.
  • the substrate is removed and rinsed with toluene and dichloromethane in sequence.
  • XPS confirms the presence of a C 60 monolayer on the treated substrate.
  • the C(ls), Os(4f) ratio increases upon C 60 self-assembly.
  • the cyclic voltammogram (not shown) of the coated substrate shows very broad, weak waves associated with sequential one electron reductions of the fullerenes.
  • vinyl ferrocene can be self-assembled by soaking an osmium covered substrate in a 5 mM solution of vinylferrocene.
  • the cyclic voltammogram of this substrate surface exhibits a reversible wave associated with ferrocene oxidation.
  • Another aspect of the invention involves chemically treating fullerenes in solution to provide a bond-forming species thereon and chemically treating the substrate surface to provide a bond-forming species effective to covalently bond with the bond-forming species of the fullerenes in solution.
  • fullerenes in solution are hydrosilated through the H 2 PtCl 6 catalyzed hydrosilation of C 60 and/or C 70 -with triethoxysilane, HSi(OEt) 3 where Et is ethyl and the hydrosilated C 60 and/or C 70 are self-assembled on a base-treated substrate surface as illustrated in FIG. 5A.
  • C 60 (30 mgrams, 0.042 mmol) and excess HSi(OEt) 3 (1.125 mmol) in toluene at 110 degrees C. for 24 hours in the presence of catalytic quantities (0.1 mgram) of H 2 PtCl 6 yields a red solution.
  • the residue contains predominantly C 60 and also significant amounts of hydrosilated fullerene derivatives; namely, C 60 H x (Si(OEt) 3 ) x where x is 1 to 6.
  • the HPLC equipment uses a Vydac reversed phase column, 4.6 mm ⁇ 25 cm, The Separations Group, 17434 Mojave St., Hesperia, Calif.
  • Spectroscopic and electrochemical data for these solution species are consistent with the C 60 H x (Si(OEt) 3 ) x formulation.
  • the 1H NMR (nuclear magnetic resonance) of the mixture is consistent with Si-H addition to the C 60 cage.
  • the cyclic voltammetry of the hydrosilated mixture containing C 60 and C 60 H x (Si(OEt) 3 ) x exhibits multiple electrochemically reversible reductions in the potential window observed for C 60 in solution (i.e. 0V to -1.9V versus Fc/Fc+) in addition to those expected for C 60 as shown in FIG. 5B (solid line).
  • the waves assigned to C 60 and C 60 H x (Si(OEt) 3 ) x overlap each other to yield a cyclic voltammogram with substantially broader waves than those observed for pure C 60 in solution, FIG. 5B (dashed line).
  • FIG. 5B solid line
  • FIG. 5C HPLC studies of the hydrosilated mixture indicates nine new compounds, C 60 H x (Si(OEt) 3 ) x and C 70 H x (Si(OEt) 3 ) x derivatives.
  • the hydrosilated C 60 and C 70 self-assemble into redox active thin films on ITO substrate surfaces.
  • an ITO substrate is soaked in a 0.5M KOH solution (EtOH/H 2 O) for three hours and then removed and rinsed with distilled water and ethanol in sequence.
  • the base-treated substrate is dried at 22 degrees C. under vacuum.
  • the base-treated substrate then is soaked in a toluene solution containing the hydrosilated fullerenes for seven days at 22 degrees C. under a nitrogen atmosphere.
  • the substrate is removed and rinsed with toluene, acetonitrile and dichloromethane in sequence.
  • the transmission UV-vis spectrum of the coated substrate exhibits broad bands that are characteristic of modified C 60 and C 70 compounds.
  • FIG. 5D (dashed line).
  • Quartz and glass may be coated with hydrosilated fullerene films in a manner similar to that described above.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Theoretical Computer Science (AREA)
  • Composite Materials (AREA)
  • Mathematical Physics (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

A method is provided for forming a fullerene layer on a substrate by chemically treating a surface of the substrate to provide a bond-forming species at the surface effective to covalently bond with fullerenes in solution and contacting the treated substrate surface with a solution of fullerenes to form a fullerene layer covalently bonded to the treated substrate surface. Alternately or in addition, a fullerene layer is formed on a substrate by chemically modifying fullerenes to provide a bond-forming species thereon, chemically treating a surface of the substrate to provide a bond-forming species effective to covalently bond with the bond-forming species of the fullerenes in solution, and contacting a solution of treated fullerenes with the treated substrate surface to form a fullerene layer covalently bonded to the treated substrate surface.
A three dimensional multilayer fullerene structure can be formed on the substrate surface by chemically modifying an initial fullerene layer formed thereon in the manner described above to provide chemical bridging species (e.g. piperazine) covalently bonded thereto and effective to covalently bond with fullerenes in solution. The modified fullerene film then is contacted with a solution of modified or unmodified fullerenes to form a second fullerene layer covalently bonded to the initial fullerene layer by the chemical bridging species. The method can be repeated to build up additional fullerene layers on the substrate surface.

Description

FIELD OF THE INVENTION
The present invention relates to the formation (self-assembly) of covalently bound mono- and multilayered fullerene films or layers on insulating, semiconducting, and metallic substrates.
BACKGROUND OF THE INVENTION
Physisorbed, multilayer films of the fullerene C60 have exhibited interesting mechanical, electrical, electrochemical, and optical properties. Such physisorbed fullerene films have been formed on substrates by the well known Langmuir-Blodgett (LB) technique and by the solution evaporation technique using C60 solutions (e.g. C60 dissolved in non-polar organic solvents such as benzene, toluene, etc.). Such physisorbed films also have been formed by thermal evaporation of solid phase fullerenes onto a suitable substrate.
However, in order to exploit the potentially useful properties of fullerene films, there is a need for a method of forming covalently bound mono- and multi-layer film structures of fullerenes on insulating, semiconducting, and metallic substrates.
It is an object of the invention to provide a method of forming monolayer and multilayer fullerene film structures on substrates chemically treated to provide a bond-forming species at the surface for covalently bonding with fullerenes in solution.
It is another object of the invention to provide a method of forming monolayer and multilayer fullerene film structures on substrates from a solution of fullerenes chemically modified to covalently bond with a treated substrate.
It is still another object of the invention to provide substrates having fullerene monolayer and multilayer film structures covalently bonded thereto.
SUMMARY OF THE INVENTION
In accordance with one aspect of the invention, a method is provided for forming a fullerene layer on a substrate by chemically treating a surface of the substrate to provide a bond-forming species at the surface effective to covalently bond with fullerenes in solution and contacting the treated substrate surface with a solution of fullerenes to form a fullerene layer covalently bonded to the treated substrate surface. In one embodiment of the invention, the substrate surface can be treated to provide a bond-forming species that forms carbon-nitrogen bonds with fullerenes in solution. For example, the substrate surface can be treated prior to contacting the solution of fullerenes to provide amine bond-forming species or sites at the treated substrate surface.
Alternately, in another embodiment of the invention, the substrate surface can be treated to provide a bond-forming species that forms a carbon-carbon bond with fullerenes in solution. For example, the substrate surface can be treated prior to contacting the solution of fullerenes to provide alkyl anion species at the treated substrate surface.
In accordance with still another embodiment of the invention, the substrate surface can be treated to provide a bond-forming species that forms a carbon-oxygen bond with fullerenes in solution. For example, the substrate surface can be treated prior to contacting the solution of fullerenes to provide transition metal oxide species at the treated substrate surface.
The fullerenes can be dissolved in a nonpolar organic solvent that is contacted with the treated substrate surface to form the fullerene layer covalently bonded to the treated substrate.
A three dimensional multilayer fullerene structure can be formed on the substrate surface by chemically modifying an initial fullerene layer formed thereon in the manner described above to provide chemical bridging species (e.g. piperazine) covalently bonded thereto and effective to covalently bond with fullerenes in solution. The modified fullerene film then is contacted with a solution of fullerenes to form a second fullerene layer covalently bonded to the initial fullerene layer by the chemical bridging species. The method can be repeated to build up additional fullerene layers on the substrate surface.
In accordance with another aspect of the invention, a method is provided for forming a fullerene layer on a substrate by chemically modifying fullerenes to provide a bond-forming species thereon, chemically treating a surface of the substrate to provide a bond-forming species effective to covalently bond with the bond-forming species of the fullerenes in solution, and contacting a solution of modified fullerenes with the treated substrate surface to form a fullerene layer covalently bonded to the treated substrate surface. For example, in one embodiment of the invention, fullerenes in solution are treated to form hydrosilated fullerenes and the substrate surface is treated to provide hydroxy groups that covalently bond with the hydrosilated fullerenes in solution. The hydrosilated fullerenes can be dissolved in a nonpolar organic solvent that is contacted with a base treated substrate surface to form the fullerene layer covalently bonded to the treated substrate.
A three dimensional multilayer fullerene structure can be formed on the substrate surface by chemically modifying an initial fullerene layer formed thereon in the manner described above to provide chemical bridging species (e.g. piperazine) covalently bonded thereto and effective to covalently bond with modified or unmodified fullerenes in solution and contacting the modified fullerene film with a suitable fullerene solution to form a second fullerene layer covalently bonded to the initial fullerene layer by the chemical bridging species.
The present invention provides in accordance with still another aspect of the invention a fullerene coated substrate having a surface treated to covalently bond with fullerene molecules and a fullerene layer covalently bonded to the treated substrate surface. The fullerene layer can be covalently bonded to the treated substrate surface by carbon-nitrogen, carbon-carbon, carbon-oxygen, and/or carbon-silicon covalent bonds. Additional fullerene layers can be covalently bonded to the fullerene layer by chemical bridging species to form multilayer fullerene structures.
The present invention also provides novel layers of fullerenes.
The aforementioned and other objects and advantages of the present invention will be better understood from the following detailed description of the invention taken with the following drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A is a cyclic voltammogram for a self assembled C60 monolayer on (MeO)3 Si(CH2)3 NH2 -treated indium-tin oxide (ITO) electrode (0.5 cm2) in CH2 Cl2 /0.1M Bu4 NPF6.
FIG. 1B is a cyclic voltammogram for a self-assembled C60 monolayer on (MeO)3 Si (CH2)3 NH2 -treated indium-tin oxide (ITO) electrode (0.8 cm2) in CH2 Cl2 /0.1M Bu4 NPF6 after refluxing in a 5 mM benzene solution of para-ferrocenylaniline for 2 days.
FIG. 1C illustrates a synthesis procedure for self-assembling C60 on an amine-modified oxide substrate surface through carbon-nitrogen bond formation.
FIG. 2A illustrates another synthesis procedure for self assembling C60 on a cysteamine/ethanethiol-modified Au substrate surface through carbon-nitrogen bond formation.
FIGS. 2B and 2C are a cyclic voltammograms for a self assembled C60 monolayer on cysteamine/ethanethiol-treated and cysteamine-2-mercaptoethanol treated Au electrodes (0.34 cm2 and 0.56 cm2) in CH2 Cl2 /0.1M Bu4 NPF6.
FIG. 3 illustrates a synthesis procedure for self-assembling C60 on a chloropropylthiol-modified metal substrate surface through carbon-carbon bond formation.
FIG. 4 illustrates a synthesis procedure for self-assembling C60 on a transition metal oxide-modified metal substrate surface through carbon-oxygen bond formation.
FIG. 5A illustrates a synthesis procedure for self assembling modified C60 /C70 fullerenes on a base-treated substrate surface through carbon-silicon bond formation.
FIGS. 5B, 5C, and 5D are cyclic voltammograms for hydrosilated C60 in solution (FIG. 5B), hydrosilated C60 /C70 in solution (FIG. 5C), and a self-assembled hydrosilated C60 monolayer (FIG. 5D) on base-treated indium-tin oxide (ITO) electrode (0.25 cm2) in CH2 Cl2 /0.1M Bu4 PF6.
DETAILED DESCRIPTION
In accordance with one aspect of the invention, a method is provided for forming a fullerene monolayer on a substrate by chemically treating a surface of the substrate to provide a bond-forming species at the surface effective to covalently bond with fullerenes in solution. The term "fullerene" as used herein is intended to include C60, C70, and other solely carbon molecules classified in the fullerene family of molecules.
In one embodiment of the invention, the substrate surface can be treated to provide a bond-forming species that forms covalent bonds with fullerenes in solution.
The following Examples 1-5 are offered to illustrate this embodiment of the invention without intending to limit the invention.
EXAMPLE 1
In this Example, the surface of an indium-tin oxide (ITO) substrate is treated to provide an amine bond-forming chemical species thereon. In particular, a base-treated (treated in 0.5M KOH ethanol/water solution for 3 hours at room temperature) ITO substrate is soaked in a 0.25M benzene solution of (MeO)3 Si(CH2)3 NH2 under reflux conditions for 8-12 hours. The substrate then is removed and rinsed with benzene, dichloromethane, and acetonitrile in sequence. The decreased hydrophilicity of the treated surface is verified with contact angle measurements (theta=46 degrees) as set forth in Table I below. Such contact angle measurements are commonly used to assess surface composition. A Rame-hart Model A-100 Goniometer was used for all contact angle measurements.
The (MeO)3 Si(CH2)3 NH2 -treated substrate then is soaked in a 1 mM benzene solution of C60 for 1-2 days under reflux conditions. The C60 dissolved in the benzene solution was obtained by the carbon arc method wherein a 1 inch diameter by 6 inches long graphite rod is arced in a water cooled vacuum arc furnace using about 10% of a 120 KW (400Amp at 300 volts DC) power source. The 1 inch diameter by 6 inches long graphite is converted to soot in 15 minutes using this procedure. The C60 and C70 fullerenes are separated from the soot chromatographically using a SOXHLET extractor with an alumina packed column. This fullerene preparation procedure is described in Nature, Vol. 347, p. 354 (1990), J. Chem. Soc. Chem. Commun., p.1423 (1990), and J. Phys. Chem., Vol. 94, p. 8630 (1990). The fullerenes used in the following Examples were obtained in the same manner.
After soaking in the C60 solution for 1-2 days, the substrate is rinsed and sonicated in benzene for 2 minutes to remove residual physisorbed C60 and then further rinsed with dichloromethane and tetrahydrofuran (THF). The relative hydrophobicity of the resulting C60 coated substrate surface is confirmed via contact angle measurements, theta=72 degrees, Table I.
              TABLE I                                                     
______________________________________                                    
Contact Angles For H.sub.2 O                                              
Surface           Contact Angle (theta)                                   
______________________________________                                    
Base-treated ITO  20 degrees                                              
(MeO).sub.3 Si(CH.sub.2).sub.3 NH.sub.2 -treated                          
                  46 degrees                                              
ITO                                                                       
C.sub.60 Monolayer on ITO                                                 
                  72 degrees                                              
HN(CH.sub.3)CH.sub.2 CH.sub.3                                             
                  63 degrees                                              
H.sub.2 N(CH.sub.2).sub.2 CH.sub.3                                        
                  60 degrees                                              
NH(CH.sub.3)CH.sub.2 CH.sub.2 OH                                          
                  42 degrees                                              
p-ferrocenylaniline                                                       
                  67 degrees                                              
______________________________________
Quartz and glass substrate surfaces can be coated with C60 in a similar manner as described for the ITO substrate surface.
The cyclic voltammetry of a (MeO)3 Si(CH2)3 NH2 -treated ITO substrate (electrode) coated with C60 in the manner described above yields the electrochemical response in CH2 Cl2 /0.1M Bu4 NPF6 as shown in FIG. 1A. The E1/2 values for the reductive waves (-1.14 and -1.51V versus ferrocene/ferrocinium, Fc/Fc+, reference potential taken with an ITO working electrode) observed in FIG. 1A are substantially more negative than the E1/2 's for the first two reductions for unmodified C60 in solution (-0.98 and -1.38V versus Fc/Fc+ as taken with an ITO working electrode), the cyclic voltammetry of C60 in solution being well known as set forth in J. Am. Chem. Soc., Vol. 113, p. 7773 (1991), J. Am. Chem. Soc., Vol. 113, p. 4364 (1991), J. Am. Chem. Soc., Vol. 113, p. 1050 (1991), and J. Am. Chem. Soc., Vol. 114, p. 3978 (1992) and exhibiting three electrochemically reversible reduction waves in the potential window between 0 and -1.9V versus Fc/Fc+.
These observed voltage shifts of -0.16V and -0.13V, respectively, for the C60 layer are consistent with the carbon-nitrogen bond forming reaction between the self-assembled C60 molecules and the underlying amine bond-forming sites. That is, the shift in E1/2 values for the C60 layer when compared with C60 in solution is consistent with a covalent carbon-nitrogen bond-forming reaction between C60 and the surface amine sites as depicted in FIG. 1C.
The resolution of the waves of FIG. 1A reflect the homogeneity of the surface fullerene species and suggests that each fullerene in the layer has a similar chemical identity, mono- and/or di-substituted adducts. Assuming each wave in FIG. 1A corresponds to a one electron transfer, integration of the current associated with the waves is consistent with monolayer coverage of the substrate surface (e.g. approximately 1.7×10-10 mol/cm2). Models based on crystallographic data for C60 predict a surface coverage of approximately 1.9×10-10 mol/cm2 for a closed packed monolayer of C60.
Importantly, the C60 layer formed in the manner described above can be chemically modified by reaction with a variety of amine reagents to build up multilayer C60 film structures. For example, referring to FIG. 1C, the steps shown can be repeated to build up a multilayer C60 structure wherein C60 layers are covalently bonded via piperazine bridging species (providing covalent carbon-nitrogen bonds) in the manner shown in FIG. 1C. The number of C60 layers formed on the substrate surface can be controlled by the number of times that the steps of FIG. 1C are repeated.
In particular, the C60 layer formed in the manner described above can be modified by reaction with amine reagents shown in Table I above. There is excellent correlation with the type of amine reacted with the C60 layer and the expected wettability of the surface obtained from such a reaction. For example, ethylmethylamine reacted with the C60 layer yields a surface with a contact angle of 63 degrees, while 2-(methylamino)ethanol reactant yields a relatively hydrophilic surface (theta=42 degrees) because of its pendant alcohol functionality.
Reaction of the C60 monolayer with para-ferrocenylaniline yields a hydrophobic surface (theta=67 degrees) with redox activity associated with the pendant ferrocene, FIG. 1B. The cyclic voltammetry of a C60 layer formed on the aforementioned amine-treated ITO substrate surface after reaction with para-ferrocenylaniline shows reductive waves (E1/2 's=-1.16V and -1.56V vs. Fc/Fc+) expected for materials containing C60 as well as an additional wave which is assigned to ferrocene oxidation (E1/2 =0.04V vs. Fc/Fc+). The surface coverage of the para-ferrocenyl aniline layer is 1.2×10-10 mol/cm2 as determined by integration of the current assigned to ferrocene oxidation, FIG. 1B. The E1/2 value for the adsorbed para-ferrocenylaniline is 0.10 V more positive than the E1/2 for para-ferrocylaniline in solution (-0.06V vs. Fc/Fc+). This shows that the NH2 of para-ferrocenylaniline has reacted with C60 and the shift in E1/2 to more positive values reflects the electron withdrawing nature of C60.
The para-ferrocenylaniline-C60 bilayer films are indefinitely stable to cycling through ferrocene oxidation, but these bi-layer films lose electrochemical activity when held at negative potentials (-1.8V) for extended periods of time. X-ray photoelectron spectroscopy (XPS) before and after electrochemical cycling of these bi-layer films confirm removal of the ferrocenylaniline and C60 layers from the substrate (electrode) surface. This is done by comparing the XPS lines of (Cls), N(ls), and Fe(2p) before and after electrochemical removal of fullerenes from the surface. This demonstrates the ability of the invention to adsorb/desorb a portion or all of the fullerene monolayer (i.e. to alter the amount of fullerine present on the substrate) by applying negative potentials to the coated substrate.
EXAMPLE 2
In this Example, the surface of a gold (Au) substrate is treated to provide a preadsorbed monolayer of NH2 CH2 CH2 SH (cysteamine) as depicted in FIG. 2A. In particular, a Au substrate (electrode) is soaked in a 1.0 mM solution of HS(CH2)2 NH2 for 24 hours. The resulting substrate is repeatedly rinsed in ethanol, CH2 Cl2 and benzene in sequence. The increased hydrophobicity of the resulting substrate surface is confirmed via contact angle measurements, Table II.
              TABLE II                                                    
______________________________________                                    
Contact Angles For H.sub.2 O                                              
Surface         Contact Angle (theta)                                     
______________________________________                                    
Au              20 degrees                                                
cysteamine-treated                                                        
                44 degrees                                                
Au                                                                        
C.sub.60 Monolayer on Au                                                  
                65 degrees                                                
______________________________________
It should be noted that the chemical adsorption of alklythiols onto Au and noble metal substrates in general is a well precedented reaction and that the adsorbates in these reactions are bound to the surface through strong covalent metal-sulfur bonds.
The cysteamine-treated Au substrate then is soaked in a 1 mM toluene solution of C60 for 24 hours at room temperature. The resulting substrate is rinsed in benzene and CH2 Cl2 to remove physisorbed C60. The increased hydrophobicity of the resulting treated surface is confirmed via contact angle measurements.
The electrochemistry of the C60 coated Au substrate surface exhibits broad features consistent with a somewhat passivated electrode surface. This is in contrast to monolayers of C60 formed in the previous Example 1, which exhibit two distinctive electrochemically reversible reductive waves under similar electrochemical conditions. The broad features appear to be due to the resistance associated with the incorporation of charge compensating ions into the hydrophobic C60 monolayer film.
Referring to FIG. 2B, the adsorption of C60 onto a premonolayer formed by soaking in a solution containing 10:1 ethanethiol:cysteamine yields the electrochemical response shown in that Figure. Two reversible waves are observed at -1.19V and -1.57V versus Fc/Fc+, which are substantially more negative than the E1/2 's for the first two reductions for unmodified C60 in solution (-0.98V and -1.38V versus Fc/Fc+). These shifts of -0.21V and -0.19V, respectively, are consistent with a bond-forming reaction between the self-assembled C60 molecules and the underlying amine sites. That is, the shift in E1/2 values for the C60 layer when compared with C60 in solution is consistent with a covalent carbon-nitrogen bond-forming reaction between C60 and the surface amine sites as depicted in FIG. 2A.
Assuming each wave in FIG. 2B corresponds to a one electron transfer, integration of the current associated with the waves is consistent with monolayer coverage of the substrate surface (e.g. approximately 1.7×10-10 mol/cm2).
The incorporation of the ethanethiol into the amine prelayer effectively dilutes the available amine sites on the substrate surface and creates more volume within the subsequently formed C60 monolayer that allows for the incorporation of charge compensating ions. It should be noted that a C60 monolayer adsorbed onto a prelayer formed from a solution containing 1:1 ethanethiol:cysteamine yields an electrochemical response similar to that for the pure cysteamine prelayers; prelayers formed from solutions containing 50:1 ethanethiol:cysteamine and then treated with C60 yield responses similar to FIG. 2B but with lower surface coverages.
A prelayer formed from a solution of 2-mercaptoethanol:cysteamine can also be used to this end.
For example, mixed solutions are prepared in different molar ratios of 2-mercaptoethanol and cysteamine. Gold substrates are immersed in these ethanol solutions at room temperature for 24 hours. The substrates are rinsed with ethanol, THF, dichloromethane, and benzene and then immersed in 1 mM benzene solutions of C60 for 24 hours. The substrate is rinsed in benzene, THF, and dichloromethane to remove physisorbed C60. FIG. 2C shows the cyclic voltammogram obtained from a substrate immersed in a 20:1 molar ratio solution of mercaptoethanol to cysteamine. Two reversible waves are observed at -1.19 and -1.55V vs. Fc/Fc+, which are substantially more negative than the E1/2 for the first two reductions of unmodified C60 in solution (E1/2 's=-0.98V and -1.38V vs. Fc/Fc+ using an ITO working electrode). These shifts of -0.21V and -0.17V respectively are consistent with a bond forming reaction between the fullerenes and the underlying amine sites. The shift in E1/2 values for the C60 layer when compared with C60 in solutions is consistent with a covalent bond forming reaction between C60 and the surface amine sites.
These results demonstrate that fullerene surface coverage can be controlled pursuant to the invention by choice and ratio of prelayer components. That is, the prelayer can comprise bond-forming species and diluant species (e.g. ethanethiol 2-mercaptoethanol, etc., present in a selected amount to control the amount of fullerene formed on the prelayer upon contact with a solution of fullerenes.
EXAMPLE 3
In this Example, the surface of a Au substrate is treated to provide an alkyl anion bond-forming chemical species thereon as shown in FIG. 3 to form a carbon-carbon bond between the fullerenes and the treated substrate. In particular, an Au electrode is soaked in a 2 mM ethanol solution of chloropropylthiol overnight at ambient temperature. The treated substrate surface is rinsed with ethanol and tetrahydrofuran. The treated substrate surface is then soaked in a 5 mM tetrahydrofuran solution of sodium naphthalide (or lithium naphthalide) at -38 degrees C. for 1 hour under a nitrogen atmosphere. After rinsing with tetrahydrofuran and benzene in sequence, the substrate is soaked in a 1 mM benzene solution of C60 for 2 hours at ambient temperature in a nitrogen atmosphere. The C60 coated Au substrate is rinsed vigorously with benzene and tetrahydrofuran in sequence. The anionic self-assembled monolayer of C60 yields an electrochemical response that is indicative of surface confined anionic C60 species (E1/2 's=-1.51V and -2.08 V versus Fc/Fc+). The anionic self-assembled monolayers of C60 can be quenched with a variety of reagents, such as CH3 CH2 OH, H2 O, CH3 I, (CH3)3 OBF4, and CF3 SO3 CH3 to form neutral C60 monolayers. These C60 monolayer films also has been characterized by XPS (XPS lines S(2p), Cl(2p), and C(1s) are compared before and after C60 self-assembly).
EXAMPLE 4
In this Example, the surface of a Au (or Pt) substrate is treated to provide transition metal oxide bond-forming species in the manner illustrated in FIG. 4 and described below. This effects a carbon-oxygen covalent bonding between the fullerenes and the treated substrate. In particular, a Au substrate is exposed to a 5 mM solution of 4-mercaptopyridine in absolute ethanol for 24 hours. This treated substrate is removed and rinsed with ethanol, benzene, and dichloromethane in sequence. The substrate then is placed in a 1 mM solution of osmium tetroxide in toluene in a dry box for 24 hours. The treated substrate is removed and rinsed with toluene, tetrahydrofuran and dichloromethane in sequence. Finally, the substrate is exposed to a 1 mM solution of C60 in toluene for 24 hours. The substrate is removed and rinsed with toluene and dichloromethane in sequence.
XPS confirms the presence of a C60 monolayer on the treated substrate. The C(ls), Os(4f) ratio increases upon C60 self-assembly. The cyclic voltammogram (not shown) of the coated substrate shows very broad, weak waves associated with sequential one electron reductions of the fullerenes.
Through reduction of OsO4 with alkenes, vinyl ferrocene can be self-assembled by soaking an osmium covered substrate in a 5 mM solution of vinylferrocene. The cyclic voltammogram of this substrate surface exhibits a reversible wave associated with ferrocene oxidation.
Another aspect of the invention involves chemically treating fullerenes in solution to provide a bond-forming species thereon and chemically treating the substrate surface to provide a bond-forming species effective to covalently bond with the bond-forming species of the fullerenes in solution.
EXAMPLE 5
In this Example, fullerenes in solution are hydrosilated through the H2 PtCl6 catalyzed hydrosilation of C60 and/or C70 -with triethoxysilane, HSi(OEt)3 where Et is ethyl and the hydrosilated C60 and/or C70 are self-assembled on a base-treated substrate surface as illustrated in FIG. 5A. In particular, C60 (30 mgrams, 0.042 mmol) and excess HSi(OEt)3 (1.125 mmol) in toluene at 110 degrees C. for 24 hours in the presence of catalytic quantities (0.1 mgram) of H2 PtCl6 yields a red solution. The mixture is filtered, and the toluene is removed from the filtrate by vacuum distillation. The resulting brown residue is washed with pentane and ether to remove excess silane. By HPLC high pressure liquid chromatography and UV-vis spectroscopy, the residue contains predominantly C60 and also significant amounts of hydrosilated fullerene derivatives; namely, C60 Hx (Si(OEt)3)x where x is 1 to 6. The HPLC equipment uses a Vydac reversed phase column, 4.6 mm×25 cm, The Separations Group, 17434 Mojave St., Hesperia, Calif. The HPLC conditions are (CH2 Cl2)C60, tRs=3.17 minute; hydrosilated mixture: C60 Hx (Si(OEt)3)x and C60, tRs=1.44, 1.60, 1.74, 1.97, 2.11, 2.27, 2.57, and 3.17 minutes, indicating seven hydrosilated fullerene species present. Spectroscopic and electrochemical data for these solution species are consistent with the C60 Hx (Si(OEt)3)x formulation. The 1H NMR (nuclear magnetic resonance) of the mixture is consistent with Si-H addition to the C60 cage.
The cyclic voltammetry of the hydrosilated mixture containing C60 and C60 Hx (Si(OEt)3)x exhibits multiple electrochemically reversible reductions in the potential window observed for C60 in solution (i.e. 0V to -1.9V versus Fc/Fc+) in addition to those expected for C60 as shown in FIG. 5B (solid line). The waves assigned to C60 and C60 Hx (Si(OEt)3)x overlap each other to yield a cyclic voltammogram with substantially broader waves than those observed for pure C60 in solution, FIG. 5B (dashed line). Because of the difficulty in separating macroscopic quantities of the C60 Hx (Si(OEt)3)x derivatives from the unreacted C60, it is difficult to obtain definitive structural data. Presumably, the hydrosilation (i.e. Si-H addition) occurs across the carbon-carbon bonds between two fused six membered rings in the fullerene structure.
Hydrosilation of a 9:1 mixture of C60 and C70 under the conditions described above yielded a mixture exhibiting different electrochemistry. For example, the voltammogram showed six discernible reversible reductions, FIG. 5C, indicating hydrosilation of the fullerenes. Three of the waves are undoubtedly due to unreacted C60 (Epc=-1.0, -1.4, -1.9V versus Fc/Fc+) but the three remaining waves appear to relate to the C60 Hx (Si(OEt)3)x and C70 Hx (Si(OEt)3)x. Although the cyclic voltammetry of C60 and C70 in solution are known to be quite similar, the cyclic voltammetry of hydrosilated C60 and hydrosilated C70 are quite different, FIG. 5B (solid line) and FIG. 5C. HPLC studies of the hydrosilated mixture indicates nine new compounds, C60 Hx (Si(OEt)3)x and C70 Hx (Si(OEt)3)x derivatives.
Importantly, the hydrosilated C60 and C70 self-assemble into redox active thin films on ITO substrate surfaces. In particular, an ITO substrate is soaked in a 0.5M KOH solution (EtOH/H2 O) for three hours and then removed and rinsed with distilled water and ethanol in sequence. The base-treated substrate is dried at 22 degrees C. under vacuum. The base-treated substrate then is soaked in a toluene solution containing the hydrosilated fullerenes for seven days at 22 degrees C. under a nitrogen atmosphere. The substrate is removed and rinsed with toluene, acetonitrile and dichloromethane in sequence. The transmission UV-vis spectrum of the coated substrate exhibits broad bands that are characteristic of modified C60 and C70 compounds. The cyclic voltammetry of the self-assembled C60 and C70 film on the substrate yields a response shown in FIG. 5D (solid line). Very broad but persistent waves are observed in the potential window between 0V and -1.6V versus Fc/Fc+. Assuming two one electron transfer processes in the potential region between 0V and -1.6V (modified forms of C60 typically have redox couples slightly more negative than that of pure C60), integration of the current associated with these waves is consistent with monolayer coverage (1.3×10-10 mols/cm2).
Scanning to more negative potentials (-2.1V) indicates additional redox activity for the fullerene film, but after one scan results in complete loss of electrochemical activity, FIG. 5D (dashed line).
Quartz and glass may be coated with hydrosilated fullerene films in a manner similar to that described above.
While the invention has been described in terms of specific embodiments thereof, it is not intended to be limited thereto but rather only to the extent set forth hereafter in the following claims.

Claims (22)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A method of forming a fullerene layer on a substrate, comprising chemically modifying a surface of the substrate to provide bond-forming species at the surface effective to covalently bond with fullerenes in solution, and contacting the treated substrate with a solution of fullerenes to form a fullerene layer covalently bonded to the chemically modified substrate surface.
2. The method of claim 1 wherein the substrate surface is chemically modified to provide bond-forming species that form carbon-nitrogen covalent bonds with fullerenes in solution.
3. The method of claim 2 wherein the substrate surface is chemically modified prior to contacting the solution of fullerenes to provide amine bond-forming species at the chemically modified substrate surface.
4. The method of claim 1 wherein the substrate surface is chemically modified to provide bond-forming species that form carbon-carbon covalent bonds with fullerenes in solution.
5. The method of claim 4 wherein the substrate surface is chemically modified prior to contacting the solution of fullerenes to provide alkyl anion bond-forming species at the chemically modified substrate surface.
6. The method of claim 1 wherein the substrate surface is chemically modified to provide bond-forming species that form carbon-oxygen covalent bonds with fullerenes in solution.
7. The method of claim 6 wherein the substrate surface is chemically modified prior to contacting the solution of fullerenes to provide mercaptopyridine-OsO4 bond-forming species at the chemically modified substrate surface.
8. The method of claim 1 wherein a solution of C60 dissolved in a organic solvent is contacted with the chemically modified substrate surface.
9. A method of forming a multilayer fullerene film on a substrate, comprising chemically modifying a surface of the substrate to provide bond-forming species at the surface effective to covalently bond with fullerenes in solution, contacting the chemically modified substrate with a solution of fullerenes to form a first fullerene layer covalently bonded to the chemically modified substrate surface, chemically modifying the first fullerene layer to provide chemical bridging species covalently bonded thereto and effective to covalently bond with fullerenes in solution, and contacting the chemically modified fullerene layer with a solution of fullerenes to form a second fullerene layer covalently bonded to the first fullerene layer by said chemical bridging species between said first and second fullerene layers.
10. The method of claim 9 wherein the substrate surface is chemically modified to provide bond-forming species that form carbon-nitrogen covalent bonds with fullerenes in solution to form said first fullerene layer.
11. The method of claim 10 wherein the substrate surface is chemically modified prior to contacting the solution of fullerenes to provide amine bond-forming species at the chemically modified substrate surface.
12. The method of claim 9 wherein the substrate surface is chemically modified to provide bond-forming species that form carbon-carbon covalent bonds with fullerenes in solution to form said first fullerene layer.
13. The method of claim 12 wherein the substrate surface is chemically modified prior to contacting the solution of fullerenes to provide alkyl anion bond-forming species at the chemically modified substrate surface.
14. The method of claim 9 wherein the substrate surface is chemically modified to provide bond-forming species that form carbon-oxygen covalent bonds with fullerenes in solution.
15. The method of claim 14 wherein the substrate surface is chemically modified prior to contacting the solution of fullerenes to provide OsO4 bond-forming species at the chemically modified substrate surface.
16. The method of claim 9 wherein the initial fullerene layer is modified to have a bifunctional piperazine covalently bonded thereto as said chemical bridging species.
17. The method of claim 9 including repeating the steps recited to form additional fullerene layers covalently bonded to a preceding fullerene layer in the modified condition.
18. A method of forming a fullerene layer on a substrate, comprising chemically modifying fullerenes to provide bond-forming species thereon, chemically modifying a surface of the substrate to provide bond-forming species effective to covalently bond with the bond-forming species of the chemically modified fullerenes in solution, and contacting a solution of the chemically modified fullerenes with the chemically modified substrate surface to form a fullerene layer covalently bonded to the chemically modified substrate surface.
19. The method of claim 18 wherein the fullerenes are chemically modified to form hydrosilated fullerenes and the substrate surface is chemically modified to provide hydroxy groups that covalently bond with the hydrosilated fullerenes in solution.
20. The method of claim 19 wherein a solution of hydrosilated C60 and/or hydrosilated C70 dissolved in a organic solvent is contacted with the hydroxy modified substrate surface.
21. A method forming a fullerene layer on a substrate, comprising chemically modifying a surface of the substrate to provide a prelayer comprising bond-forming species and diluant species present in an amount to control the amount of fullerenes bonded to the prelayer and contacting the prelayer with a solution of fullerenes to bond fullerenes to said bond-forming species of said prelayer.
22. A method of modifying a fullerene layer covalently bonded to a substrate, comprising subjecting the fullerene layer to a negative potential to desorb an amount of fullerenes covalently bonded to the substrate.
US08/016,820 1993-02-10 1993-02-10 Method of forming self-assembled, mono- and multi-layer fullerene film and coated substrates produced thereby Expired - Fee Related US5338571A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US08/016,820 US5338571A (en) 1993-02-10 1993-02-10 Method of forming self-assembled, mono- and multi-layer fullerene film and coated substrates produced thereby

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US08/016,820 US5338571A (en) 1993-02-10 1993-02-10 Method of forming self-assembled, mono- and multi-layer fullerene film and coated substrates produced thereby

Publications (1)

Publication Number Publication Date
US5338571A true US5338571A (en) 1994-08-16

Family

ID=21779154

Family Applications (1)

Application Number Title Priority Date Filing Date
US08/016,820 Expired - Fee Related US5338571A (en) 1993-02-10 1993-02-10 Method of forming self-assembled, mono- and multi-layer fullerene film and coated substrates produced thereby

Country Status (1)

Country Link
US (1) US5338571A (en)

Cited By (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0743103A1 (en) * 1995-05-19 1996-11-20 Marijan Bradic Uses of polyfluorofullerenes for the coating of surfaces of tools
US5580612A (en) * 1992-08-06 1996-12-03 Hoechst Aktiengesellschaft Process for production of layer element containing at least one monomolecular layer of an amphiphilic molecule and one fullerene
US5622800A (en) * 1993-10-22 1997-04-22 Canon Kabushiki Kaisha Electrophotographic photosensitive member, electrophotographic apparatus and apparatus unit including the photosensitive member
WO1997038802A1 (en) * 1996-04-12 1997-10-23 The Texas A & M University System Polymeric self-assembled mono- and multilayers and their use in photolithography
WO1998009913A1 (en) * 1996-09-06 1998-03-12 University Of Massachusetts Reversible covalent attachment of fullerenes to insoluble supports
WO1999026729A1 (en) * 1997-11-21 1999-06-03 Universite De Montreal Assembly of polythiophene derivative on a self-assembled monolayer (sam)
US6183714B1 (en) 1995-09-08 2001-02-06 Rice University Method of making ropes of single-wall carbon nanotubes
US6277438B1 (en) * 1999-05-03 2001-08-21 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Protective fullerene (C60) packaging system for microelectromechanical systems applications
WO2001023962A3 (en) * 1999-09-24 2002-01-10 Univ Heidelberg Surface-modified layer system
US20020117177A1 (en) * 1996-12-02 2002-08-29 Kwok Philip Rodney Harness assembly for a nasal mask
EP1090077A4 (en) * 1998-05-27 2003-06-11 Commw Scient Ind Res Org MOLECULAR COATINGS
WO2003065881A2 (en) 2002-02-06 2003-08-14 Orbus Medical Technologies Inc. Medical device with coating that promotes endothelial cell adherence and differentiation
US20030198021A1 (en) * 2002-04-23 2003-10-23 Freedman Philip D. Structure with heat dissipating device and method to produce a computer
US20030229393A1 (en) * 2001-03-15 2003-12-11 Kutryk Michael J. B. Medical device with coating that promotes cell adherence and differentiation
US6793967B1 (en) * 1999-06-25 2004-09-21 Sony Corporation Carbonaceous complex structure and manufacturing method therefor
US6805904B2 (en) 2002-02-20 2004-10-19 International Business Machines Corporation Process of forming a multilayer nanoparticle-containing thin film self-assembly
US20050043787A1 (en) * 2000-03-15 2005-02-24 Michael John Bradley Kutryk Medical device with coating that promotes endothelial cell adherence
US20050100497A1 (en) * 1995-09-08 2005-05-12 William Marsh Rice University Electrical conductors comprising single-wall carbon nanotubes
US20050221184A1 (en) * 2002-10-04 2005-10-06 Mitsubishi Chemical Corporation Additive for anode material for lithium secondary battery, anode material for lithium secondary battery, anode and lithium secondary battery using the anode material for lithium secondary battery
US20060121012A1 (en) * 2000-03-15 2006-06-08 Orbus Medical Technologies, Inc. Medical device with coating for capturing genetically-altered cells and methods of using same
US7071047B1 (en) 2005-01-28 2006-07-04 International Business Machines Corporation Method of forming buried isolation regions in semiconductor substrates and semiconductor devices with buried isolation regions
US20060155376A1 (en) * 2005-01-13 2006-07-13 Blue Membranes Gmbh Composite materials containing carbon nanoparticles
US20060167147A1 (en) * 2005-01-24 2006-07-27 Blue Membranes Gmbh Metal-containing composite materials
US20060185794A1 (en) * 2005-02-24 2006-08-24 Ayers Michael Raymond Porous films and bodies with enhanced mechanical strength
US20060228828A1 (en) * 2005-04-11 2006-10-12 Miller Seth A Versatile system for selective organic structure production
US20070003749A1 (en) * 2005-07-01 2007-01-04 Soheil Asgari Process for production of porous reticulated composite materials
US20070042017A1 (en) * 2000-03-15 2007-02-22 Orbus Medical Technologies, Inc. Medical device with coating that promotes endothelial cell adherence and differentiation
US20070122622A1 (en) * 2002-04-23 2007-05-31 Freedman Philip D Electronic module with thermal dissipating surface
US20070128723A1 (en) * 2000-03-15 2007-06-07 Orbusneich Medical, Inc. Progenitor Endothelial Cell Capturing with a Drug Eluting Implantable Medical Device
US20070141107A1 (en) * 2000-03-15 2007-06-21 Orbusneich Medical, Inc. Progenitor Endothelial Cell Capturing with a Drug Eluting Implantable Medical Device
US20080020197A1 (en) * 2006-05-31 2008-01-24 Roskilde Semiconductor Llc Porous inorganic solids for use as low dielectric constant materials
WO2007143026A3 (en) * 2006-05-31 2008-02-28 Michael Raymond Ayers Linked periodic networks of alternating carbon and inorganic clusters for use as low dielectric constant materials
EP1548862A4 (en) * 2002-10-04 2009-04-22 Mitsubishi Chem Corp MATERIAL AND ADDITIVE FOR LITHIUM ACCUMULATOR CATHODE MATERIAL, CORRESPONDING USES, CATHODE AND LITHIUM ACCUMULATOR THUS OBTAINED
EP1560282A4 (en) * 2002-10-31 2009-04-29 Mitsubishi Chem Corp POSITIVE ELECTRODE MATERIAL FOR A LITHIUM SECONDARY BATTERY AND POSITIVE ELECTRODE AND LITHIUM SECONDARY BATTERY OBTAINED FROM SUCH MATERIAL
US7790234B2 (en) 2006-05-31 2010-09-07 Michael Raymond Ayers Low dielectric constant materials prepared from soluble fullerene clusters
US7883742B2 (en) 2006-05-31 2011-02-08 Roskilde Semiconductor Llc Porous materials derived from polymer composites
US8088060B2 (en) 2000-03-15 2012-01-03 Orbusneich Medical, Inc. Progenitor endothelial cell capturing with a drug eluting implantable medical device
US9522217B2 (en) 2000-03-15 2016-12-20 Orbusneich Medical, Inc. Medical device with coating for capturing genetically-altered cells and methods for using same
CN112941906A (en) * 2021-03-03 2021-06-11 厦门福纳新材料科技有限公司 Fullerene composite fiber fabric and preparation method thereof
CN115845638A (en) * 2022-11-24 2023-03-28 河海大学 Modified polyvinylidene fluoride composite membrane for membrane distillation and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5178980A (en) * 1991-09-03 1993-01-12 Xerox Corporation Photoconductive imaging members with a fullerene compound

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5178980A (en) * 1991-09-03 1993-01-12 Xerox Corporation Photoconductive imaging members with a fullerene compound

Non-Patent Citations (96)

* Cited by examiner, † Cited by third party
Title
( 2 C 70 ) Ir(CO)Cl(PPh 3 ) 2 : The Synthesis and Structure of an Organometallic Derivative of a Higher Fullerene; J. Am. Chem. Soc. 1991, 113, pp. 8953 8955; Balch, Catalano, Lee, Olmstead. (no mo.). *
(Rb x K 1 x ) 3 C 60 Superconductors; Formation of a Continuous Series of Solid Solutions; Science, vol. 253, pp. 886 888; Chen, Kelty and Lieber. (no date). *
(Rbx K1-x)3 C60 Superconductors; Formation of a Continuous Series of Solid Solutions; Science, vol. 253, pp. 886-888; Chen, Kelty and Lieber. (no date).
(η2-C70) Ir(CO)Cl(PPh3)2 : The Synthesis and Structure of an Organometallic Derivative of a Higher Fullerene; J. Am. Chem. Soc. 1991, 113, pp. 8953-8955; Balch, Catalano, Lee, Olmstead. (no mo.).
A quartz crystal microbalance analysis of ion insertion into WO 3 ; Solar Energy Mat. 25 (1992) pp. 269 291; Babinec. (no no.). *
A quartz crystal microbalance analysis of ion insertion into WO3 ; Solar Energy Mat. 25 (1992) pp. 269-291; Babinec. (no no.).
A Simple Sozhlet Chrmatographic Method for the Isolation of Pure C 60 and C 70 ; J. Org. Chem. 1992, 57, pp. 3254 3256; Khemani, Prato and Wudl. (no mo.). *
A Simple Sozhlet Chrmatographic Method for the Isolation of Pure C60 and C70 ; J. Org. Chem. 1992, 57, pp. 3254-3256; Khemani, Prato and Wudl. (no mo.).
Accumulating Evidence for the Selective Reactivity of the 6 6 Ring Fusion of C 60 . Preparation of Structure of ( 2 C 60 ) Ir(CO)Cl)PPh 3 ) 2 5C 6 H 6 ; Inorg. Chem. 1991, 30, pp. 3980 3981. (no mo.). *
Accumulating Evidence for the Selective Reactivity of the 6-6 Ring Fusion of C60. Preparation of Structure of (η2-C60) Ir(CO)Cl)PPh3)2 -5C6 H6 ; Inorg. Chem. 1991, 30, pp. 3980-3981. (no mo.).
Characterization of the Soluble All Carbon Molecules C 60 and C 70 ; J. Phys. Chem. 1990, pp. 8630 8633; Ajie, Alvarez, Anz, Beck Diederich, Fostiropoulos, Huffman, Kraetschmer, Rubin, etc. (no mo.). *
Characterization of the Soluble All-Carbon Molecules C60 and C70 ; J. Phys. Chem. 1990, pp. 8630-8633; Ajie, Alvarez, Anz, Beck Diederich, Fostiropoulos, Huffman, Kraetschmer, Rubin, etc. (no mo.).
Chemically Modified Tin Oxide Electrode; Chemistry, vol. 47, Oct. 12, 1975, pp. 1882 1886; Moses, Wier, Murray. *
Chemically Modified Tin Oxide Electrode; Chemistry, vol. 47, Oct. 12, 1975, pp. 1882-1886; Moses, Wier, Murray.
Covalently Attached Organic Monolayers on Semiconductor Surfaces; J. Am. Chem. Soc. 1978, 100, pp. 8050 8055; Haller. (no mo.). *
Covalently Attached Organic Monolayers on Semiconductor Surfaces; J. Am. Chem. Soc. 1978, 100, pp. 8050-8055; Haller. (no mo.).
Crystal Structure of Osmylated C 60 : Confirmation of the Soccer Ball Framework; Science, vol. 252, pp. 312 313; Hawkins, Meyer, Lewis, Loren, Hollander. (no date). *
Crystal Structure of Osmylated C60 : Confirmation of the Soccer Ball Framework; Science, vol. 252, pp. 312-313; Hawkins, Meyer, Lewis, Loren, Hollander. (no date).
Electrochemical Applications of the Quartz Crystal Microbalance; Anal. Chem. Vol. 61, No. 20, Oct. 15,1989, pp. 1147 1154; Deakin and Buttry. *
Electrochemical Applications of the Quartz Crystal Microbalance; Anal. Chem. Vol. 61, No. 20, Oct. 15,1989, pp. 1147-1154; Deakin and Buttry.
Electrochemical Detection of C 60 6 and C 70 6 : Enhanced Stability of Fullerides in Solution; J. Am. Chem. Soc. 1992, 114, pp. 3978 3980; Xie, Perez Cordero and Echegoyen. (no mo.). *
Electrochemical detection of C 60 6 at Low Temperature J. Chem. Soc., Chem. Commun. 1992, pp. 781 782; Ohsawa and Saji. (no mo.). *
Electrochemical Detection of C606- and C706- : Enhanced Stability of Fullerides in Solution; J. Am. Chem. Soc. 1992, 114, pp. 3978-3980; Xie, Perez-Cordero and Echegoyen. (no mo.).
Electrochemical detection of C606- at Low Temperature J. Chem. Soc., Chem. Commun. 1992, pp. 781-782; Ohsawa and Saji. (no mo.).
Electrochemical Detection of Fulleronium and Highly Reduced Fulleride (C 60 5 ) Ions in Solution; J. Am. Chem. Soc. 1991, 113, pp. 7773 7774, Dubois, Kadish, Flannagan and Wilson. (no mo.). *
Electrochemical Detection of Fulleronium and Highly Reduced Fulleride (C605- ) Ions in Solution; J. Am. Chem. Soc. 1991, 113, pp. 7773-7774, Dubois, Kadish, Flannagan and Wilson. (no mo.).
Electrochemical Reduction and Oxidation of C 60 Films; J. Am. Chem. Soc. 1991, 113, pp. 5456 5457; Jehoulet and Bard. (no mo.). *
Electrochemical Reduction and Oxidation of C60 Films; J. Am. Chem. Soc. 1991, 113, pp. 5456.5457; Jehoulet and Bard. (no mo.).
Electrochemistry and Langmuir Trough Studies of C 60 and C 70 Films: J. Am. Chem. Soc. 1992, 114, 4237 4247; Jehoulet, Obeng, Kim, Zhou and Bard. (no mo.). *
Electrochemistry and Langmuir Trough Studies of C60 and C70 Films: J. Am. Chem. Soc. 1992, 114, 4237-4247; Jehoulet, Obeng, Kim, Zhou and Bard. (no mo.).
Electrochemistry at the Water/Air Interface. Lateral Electron Transport in Langmuir Monolayers; J. Am. Chem. Soc. 1988, 110, pp. 2009 2011; Widrig, Miller and Majda. (no mo.). *
Electrochemistry at the Water/Air Interface. Lateral Electron Transport in Langmuir Monolayers; J. Am. Chem. Soc. 1988, 110, pp. 2009-2011; Widrig, Miller and Majda. (no mo.).
Electrochemistry of Chemisorbed Molecules. I. Reactants Connected to Electrodes through Olefinic Substituents; J. Phys. Chem. vol. 77, No. 11, 1973, pp. 1401 1410; Lane and Hubbard. (no mo.). *
Electrochemistry of Chemisorbed Molecules. I. Reactants Connected to Electrodes through Olefinic Substituents; J. Phys. Chem. vol. 77, No. 11, 1973, pp. 1401-1410; Lane and Hubbard. (no mo.).
Formation of Langmuir Blodgett Films of a Fullerene; J. Am. Chem. Soc. 1992, pp. 4 6; Nakamura, Tachibana, Yumura, Matsumoto, Azumi, Tanaka and Kawabata. (no mo.). *
Formation of Langmuir-Blodgett Films of a Fullerene; J. Am. Chem. Soc. 1992, pp. 4-6; Nakamura, Tachibana, Yumura, Matsumoto, Azumi, Tanaka and Kawabata. (no mo.).
Formation of Monolayer Films by the Spontaneous Assembly of Organic Thiols from Solution onto Gold; J. A. Chem. Soc. 1989, 111, pp. 321 334; Bain, Throughton, Tao, Evall, Whitesides, etc. (no mo.). *
Formation of Monolayer Films by the Spontaneous Assembly of Organic Thiols from Solution onto Gold; J. A. Chem. Soc. 1989, 111, pp. 321-334; Bain, Throughton, Tao, Evall, Whitesides, etc. (no mo.).
Formation of Multilayers by Self Assembly; Langmuir, 1989, 5, pp. 101 111; Tillman, Ulman and Penner. (no mo.). *
Formation of Multilayers by Self-Assembly; Langmuir, 1989, 5, pp. 101-111; Tillman, Ulman and Penner. (no mo.).
Fullerene Self Assembly onto (MeO) 3 Si(CH 2 ( 3 NH 2 Modified Oxide Surfaces; J. Am. Chem. Soc. 1993, 115, pp. 1193 1194; Chen, Caldwell and Mirkin (no mo.). *
Fullerene Self-Assembly onto (MeO)3 Si(CH2 (3 NH2 -Modified Oxide Surfaces; J. Am. Chem. Soc. 1993, 115, pp. 1193-1194; Chen, Caldwell and Mirkin (no mo.).
Globe trotting Hydrogens on the Surface of the Fullerence Compound C 60 H 6 (N(CH 2 CH 2 ) 2 O) 6 ; Angew. Chem. Int. Ed. Engl. 30 (1990) No. 10, pp. 1309 1310; Hirsch, Li and Wudl. (no mo.). *
Globe-trotting Hydrogens on the Surface of the Fullerence Compound C60 H6 (N(CH2 CH2)2 O)6 ; Angew. Chem. Int. Ed. Engl. 30 (1990) No. 10, pp. 1309-1310; Hirsch, Li and Wudl. (no mo.).
Homogeneous Catalysis of Hydrosilation by Transition Metals; Adv. Org. Chem., vol. 17, pp. 407 447; Speier. (no date). *
Homogeneous Catalysis of Hydrosilation by Transition Metals; Adv. Org. Chem., vol. 17, pp. 407-447; Speier. (no date).
Immobilization of Monomolecular Layers on Electrodes; <<Molecular Design of Electrode Surfaces>>, pp. 12-21; Edited by Royce Murray. (no date).
Immobilization of Monomolecular Layers on Electrodes; Molecular Design of Electrode Surfaces , pp. 12 21; Edited by Royce Murray. (no date). *
Incorporation of Phenoxy Groups in Self Assembled Monolayers of Trichlorosilane Derivatives; Effects on Film Thickness, Wettability, and Molecular Orientation; J. Am. Chem. Soc. 1988, 110, pp. 6136 6144; Tillman, Ulman, Schidkraut and Penner. (no mo.). *
Incorporation of Phenoxy Groups in Self-Assembled Monolayers of Trichlorosilane Derivatives; Effects on Film Thickness, Wettability, and Molecular Orientation; J. Am. Chem. Soc. 1988, 110, pp. 6136-6144; Tillman, Ulman, Schidkraut and Penner. (no mo.).
Ionic Interactions Play a Major Role in Determining the Electrochemical Behavior of Self Assembling Viologen Monolayers; Langmuir 1990, 6, pp. 1319 1322; De Long and Buttry. (no mo.). *
Ionic Interactions Play a Major Role in Determining the Electrochemical Behavior of Self-Assembling Viologen Monolayers; Langmuir 1990, 6, pp. 1319-1322; De Long and Buttry. (no mo.).
Isolation, Separation and Characterisation of the Fullerenes C 60 and C 70 : The Third Form of Carbon; J. Chem. Soc., Chem. Commun. 1990, pp. 1423 1425; Taylor, Hare, Abdul Sada and Kroto. (no mo.). *
Isolation, Separation and Characterisation of the Fullerenes C60 and C70 : The Third Form of Carbon; J. Chem. Soc., Chem. Commun. 1990, pp. 1423-1425; Taylor, Hare, Abdul-Sada and Kroto. (no mo.).
Langmuir Films of C 60 At the Air Water Interface; J. Am. Chem. Soc. 1991, 113, pp. 6279 6280; Obeng and Bard. (no mo.). *
Langmuir Films of C60 At the Air-Water Interface; J. Am. Chem. Soc. 1991, 113, pp. 6279-6280; Obeng and Bard. (no mo.).
Large second harmonic response of C 60 thin films; App. Phys. Lett. 60 (7), Feb. 17, 1992, pp. 810 812; Wang, Zhang, Lin, Liu, Wong, Kappes, Chang and Ketterson. *
Large second-harmonic response of C60 thin films; App. Phys. Lett. 60 (7), Feb. 17, 1992, pp. 810-812; Wang, Zhang, Lin, Liu, Wong, Kappes, Chang and Ketterson.
Luminescence and Absorption Spectra of C 60 Films; J. Phys. Chem. 1991, 95, pp. 2127 2129; Reber, Yee, McKiernan, Zink, Williams, Tong, Ohlberg, Whetten, and Diederich. (no mo.). *
Luminescence and Absorption Spectra of C60 Films; J. Phys. Chem. 1991, 95, pp. 2127-2129; Reber, Yee, McKiernan, Zink, Williams, Tong, Ohlberg, Whetten, and Diederich. (no mo.).
Metal Complexes of Buckminsterfullerence (C 60 ); Acc. Chem. Res. 1992, 25, pp. 134 142; Fagan, Calabrese and Malone. (no mo.). *
Metal Complexes of Buckminsterfullerence (C60); Acc. Chem. Res. 1992, 25, pp. 134-142; Fagan, Calabrese and Malone. (no mo.).
Modeling Organic Surfaces with Self Assembled Monolayers; Angew, Chem. Int. Ed. Engl. 28 (1989) No. 4, pp. 506 512; Bain and Whitesides. (no mo.). *
Modeling Organic Surfaces with Self-Assembled Monolayers; Angew, Chem. Int. Ed. Engl. 28 (1989) No. 4, pp. 506-512; Bain and Whitesides. (no mo.).
Organic Chemistry of C 60 (Buckminsterfullerence): Chromatography and Osmylation; J. Org. Chem. 1990, pp. 6250 6262; Hawkins, Lewis, Loren, Meyer, Heath, Shibato and Saykally. (no mo.). *
Organic Chemistry of C60 (Buckminsterfullerence): Chromatography and Osmylation; J. Org. Chem. 1990, pp. 6250-6262; Hawkins, Lewis, Loren, Meyer, Heath, Shibato and Saykally. (no mo.).
Organometallic Chemistry with Buckmnsterfullerene. Preparation and Properties of an Indenyliridium (I) Complex; J. Am. Chem. Soc. 1991, 113, pp. 8957 8958; Koefod, Hudgens and Shapley (no mo.). *
Organometallic Chemistry with Buckmnsterfullerene. Preparation and Properties of an Indenyliridium (I) Complex; J. Am. Chem. Soc. 1991, 113, pp. 8957-8958; Koefod, Hudgens and Shapley (no mo.).
Penetration Controlled Reactions in Organized Monolayer Assemblies. 1. Aqueous Permanganate Interaction with Monolayer and Multilayer Films of Long Chain Surfactants; Langmuir, 1987, 3, pp. 1034 1044; Maoz and Sagiv. (no mo.). *
Penetration Controlled Reactions in Organized Monolayer Assemblies. 2. Aqueous Permanganate Interaction with Self Assembling Monolayers of Long Chain Surfactants; Langmuir 1987, 3, pp. 1045 1051; Maoz and Sagiv. (no mo.). *
Penetration-Controlled Reactions in Organized Monolayer Assemblies. 1. Aqueous Permanganate Interaction with Monolayer and Multilayer Films of Long-Chain Surfactants; Langmuir, 1987, 3, pp. 1034-1044; Maoz and Sagiv. (no mo.).
Penetration-Controlled Reactions in Organized Monolayer Assemblies. 2. Aqueous Permanganate Interaction with Self-Assembling Monolayers of Long-Chain Surfactants; Langmuir 1987, 3, pp. 1045-1051; Maoz and Sagiv. (no mo.).
Photoelectrochemical Behaviour of C 60 Films; J. Am. Chem. Soc. 1991, 113, pp. 6291 6293; Miller, Rosamilia, Dabbagh, Tycko, Haddon, Muller, Wilson, Murphy and Hebard. (no mo.). *
Photoelectrochemical Behaviour of C60 Films; J. Am. Chem. Soc. 1991, 113, pp. 6291-6293; Miller, Rosamilia, Dabbagh, Tycko, Haddon, Muller, Wilson, Murphy and Hebard. (no mo.).
Preparation and structure of the alkali metal fulleride A 4 C 60 ; Nature, vol. 352, Aug. 22, 1991, pp. 701 703; Fleming, Rosseinsky, Ramirez, Murphy, Tully, Haddon, Siegrist, Tycko, etc. *
Preparation and structure of the alkali-metal fulleride A4 C60 ; Nature, vol. 352, Aug. 22, 1991, pp. 701-703; Fleming, Rosseinsky, Ramirez, Murphy, Tully, Haddon, Siegrist, Tycko, etc.
Reaction of C 60 with Dimethyldioxirane Formation of an Epoxide and a 1,3 Dioxolane Derivative; Angew, Chem. Int. Ed. Engl. 31 (1992) No. 3, pp. 351 353; Elemes, Silverman, Sheu, Kao, etc. (no mo.). *
Reaction of C60 with Dimethyldioxirane-Formation of an Epoxide and a 1,3-Dioxolane Derivative; Angew, Chem. Int. Ed. Engl. 31 (1992) No. 3, pp. 351-353; Elemes, Silverman, Sheu, Kao, etc. (no mo.).
Solid C 60 : A New Form of Carbon; Nature, vol. 347, Sep. 27, 1990, pp. 354 358; Kraetschmer, Lamb, Fostiropoulos and Huffman. *
Solid C60 : A New Form of Carbon; Nature, vol. 347, Sep. 27, 1990, pp. 354-358; Kraetschmer, Lamb, Fostiropoulos and Huffman.
Spectroelectrochemical Study of the C 60 and C 70 Fullerenes and Their Mono , Di , Tri , and Tetraanions; J. Am. Chem. Soc., 1991, 113, pp. 4364 4366; Dubois, Kadish, Flanagan, Haufler, Chibante (no mo.). *
Spectroelectrochemical Study of the C60 and C70 Fullerenes and Their Mono-, Di-, Tri-, and Tetraanions; J. Am. Chem. Soc., 1991, 113, pp. 4364-4366; Dubois, Kadish, Flanagan, Haufler, Chibante (no mo.).
Superconductivity at 45 K in Rb/T1 Codoped C 60 and C 60 /C 70 Mixtures; Science, vol. 254, pp. 826 829; Iqbal, Baughman, Ramakrishna, Khare, Murphy, Bornemman and Morirs. (no date). *
Superconductivity at 45 K in Rb/T1 Codoped C60 and C60 /C70 Mixtures; Science, vol. 254, pp. 826-829; Iqbal, Baughman, Ramakrishna, Khare, Murphy, Bornemman and Morirs. (no date).
Superconductivity at 8.4 K in calcium doped C 60 ; Nature, vol. 355, Feb. 6, 1992, pp. 529 531; Kortan, Kopylov, Glarum, Gyorgy, Ramirez, Fleming, Thiel and Haddon. *
Superconductivity at 8.4 K in calcium-doped C60 ; Nature, vol. 355, Feb. 6, 1992, pp. 529-531; Kortan, Kopylov, Glarum, Gyorgy, Ramirez, Fleming, Thiel and Haddon.
Superconductivity of 18K in potassium doped C 60 ; Nature, vol. 350, Apr. 18, 1991, pp. 600 601; Hebard, Rosseinsky; Haddon, Murphy, Glarum, Palstra, Ramirez and Kortan. *
Superconductivity of 18K in potassium-doped C60 ; Nature, vol. 350, Apr. 18, 1991, pp. 600-601; Hebard, Rosseinsky; Haddon, Murphy, Glarum, Palstra, Ramirez and Kortan.
Systematic Inflation of Buckminsterfullerene C 60 : Synthesis of Diphenyl Fulleroids C 61 to C 66 ; Science, vol. 254, pp. 1186 1188 Suzuki, Li, Khemain, Wudl, and Almarsson. (no date). *
Systematic Inflation of Buckminsterfullerene C60 : Synthesis of Diphenyl Fulleroids C61 to C66 ; Science, vol. 254, pp. 1186-1188 Suzuki, Li, Khemain, Wudl, and Almarsson. (no date).
The Chemical Properties of Buckminsterfullerence (C 60 ) and the Birth and Infancy of Fulleroids; Acc. Chem. Res. 1992, 25, pp. 157 161; Wudl. (no mo.). *
The Chemical Properties of Buckminsterfullerence (C60) and the Birth and Infancy of Fulleroids; Acc. Chem. Res. 1992, 25, pp. 157-161; Wudl. (no mo.).
The Structure of the C 60 Molecule: X Ray Crystal Structure Determination of a Twin at 110 K; Science, vo. 254, pp. 408 410; Liu, Lu, Kappes and Ibers. (no date). *
The Structure of the C60 Molecule: X-Ray Crystal Structure Determination of a Twin at 110 K; Science, vo. 254, pp. 408-410; Liu, Lu, Kappes and Ibers. (no date).
Two Different Fullerenes Have the Same Cyclic Voltammetry; J. Am. Chem. Soc. 1991, 113, pp. 1050 1051; Allemand, Koch, etc. (no mo.). *
Two Different Fullerenes Have the Same Cyclic Voltammetry; J. Am. Chem. Soc. 1991, 113, pp. 1050-1051; Allemand, Koch, etc. (no mo.).

Cited By (69)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5580612A (en) * 1992-08-06 1996-12-03 Hoechst Aktiengesellschaft Process for production of layer element containing at least one monomolecular layer of an amphiphilic molecule and one fullerene
US5622800A (en) * 1993-10-22 1997-04-22 Canon Kabushiki Kaisha Electrophotographic photosensitive member, electrophotographic apparatus and apparatus unit including the photosensitive member
EP0743103A1 (en) * 1995-05-19 1996-11-20 Marijan Bradic Uses of polyfluorofullerenes for the coating of surfaces of tools
EP0743102A1 (en) * 1995-05-19 1996-11-20 Marijan Bradic Uses of polyfluorofullerenes for the coating of surfaces of materials
US7338915B1 (en) 1995-09-08 2008-03-04 Rice University Ropes of single-wall carbon nanotubes and compositions thereof
US20050100497A1 (en) * 1995-09-08 2005-05-12 William Marsh Rice University Electrical conductors comprising single-wall carbon nanotubes
US6183714B1 (en) 1995-09-08 2001-02-06 Rice University Method of making ropes of single-wall carbon nanotubes
US6969504B2 (en) 1995-09-08 2005-11-29 William Marsh Rice University Electrical conductors comprising single-wall carbon nanotubes
US20060008407A1 (en) * 1995-09-08 2006-01-12 William Marsh Rice University Ropes of single-wall carbon nanotubes
US7070754B2 (en) 1995-09-08 2006-07-04 William Marsh Rice University Ropes of single-wall carbon nanotubes
WO1997038802A1 (en) * 1996-04-12 1997-10-23 The Texas A & M University System Polymeric self-assembled mono- and multilayers and their use in photolithography
US5885753A (en) * 1996-04-12 1999-03-23 The Texas A&M University System Polymeric self-assembled mono- and multilayers and their use in photolithography
WO1998009913A1 (en) * 1996-09-06 1998-03-12 University Of Massachusetts Reversible covalent attachment of fullerenes to insoluble supports
US20020117177A1 (en) * 1996-12-02 2002-08-29 Kwok Philip Rodney Harness assembly for a nasal mask
WO1999026729A1 (en) * 1997-11-21 1999-06-03 Universite De Montreal Assembly of polythiophene derivative on a self-assembled monolayer (sam)
EP1090077A4 (en) * 1998-05-27 2003-06-11 Commw Scient Ind Res Org MOLECULAR COATINGS
US6277438B1 (en) * 1999-05-03 2001-08-21 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Protective fullerene (C60) packaging system for microelectromechanical systems applications
US6793967B1 (en) * 1999-06-25 2004-09-21 Sony Corporation Carbonaceous complex structure and manufacturing method therefor
US6815067B2 (en) * 1999-06-25 2004-11-09 Sony Corporation Carbonaceous complex structure and manufacturing method therefor
WO2001023962A3 (en) * 1999-09-24 2002-01-10 Univ Heidelberg Surface-modified layer system
US6764758B1 (en) 1999-09-24 2004-07-20 Universitat Heidelberg Surface-modified layer system
US20050043787A1 (en) * 2000-03-15 2005-02-24 Michael John Bradley Kutryk Medical device with coating that promotes endothelial cell adherence
US8088060B2 (en) 2000-03-15 2012-01-03 Orbusneich Medical, Inc. Progenitor endothelial cell capturing with a drug eluting implantable medical device
US20070141107A1 (en) * 2000-03-15 2007-06-21 Orbusneich Medical, Inc. Progenitor Endothelial Cell Capturing with a Drug Eluting Implantable Medical Device
US20070128723A1 (en) * 2000-03-15 2007-06-07 Orbusneich Medical, Inc. Progenitor Endothelial Cell Capturing with a Drug Eluting Implantable Medical Device
US20070055367A1 (en) * 2000-03-15 2007-03-08 Orbus Medical Technologies, Inc. Medical device with coating that promotes endothelial cell adherence and differentiation
US20070042017A1 (en) * 2000-03-15 2007-02-22 Orbus Medical Technologies, Inc. Medical device with coating that promotes endothelial cell adherence and differentiation
US7037332B2 (en) 2000-03-15 2006-05-02 Orbus Medical Technologies, Inc. Medical device with coating that promotes endothelial cell adherence
US20060121012A1 (en) * 2000-03-15 2006-06-08 Orbus Medical Technologies, Inc. Medical device with coating for capturing genetically-altered cells and methods of using same
US20060135476A1 (en) * 2000-03-15 2006-06-22 Orbus Medical Technologies, Inc. Medical device with coating that promotes endothelial cell adherence and differentiation
US7803183B2 (en) 2000-03-15 2010-09-28 Orbusneich Medical, Inc. Medical device with coating that promotes endothelial cell adherence
US9522217B2 (en) 2000-03-15 2016-12-20 Orbusneich Medical, Inc. Medical device with coating for capturing genetically-altered cells and methods for using same
US9364565B2 (en) 2000-03-15 2016-06-14 Orbusneich Medical, Inc. Medical device with coating for capturing genetically-altered cells and methods of using same
US8460367B2 (en) 2000-03-15 2013-06-11 Orbusneich Medical, Inc. Progenitor endothelial cell capturing with a drug eluting implantable medical device
US20030229393A1 (en) * 2001-03-15 2003-12-11 Kutryk Michael J. B. Medical device with coating that promotes cell adherence and differentiation
WO2003065881A2 (en) 2002-02-06 2003-08-14 Orbus Medical Technologies Inc. Medical device with coating that promotes endothelial cell adherence and differentiation
WO2003065881A3 (en) * 2002-02-06 2003-10-30 Orbus Medical Technologies Inc Medical device with coating that promotes endothelial cell adherence and differentiation
CN100455275C (en) * 2002-02-06 2009-01-28 祥丰医疗有限公司 Medical device coated with a coating that promotes endothelial cell adhesion and differentiation
US20050009079A1 (en) * 2002-02-20 2005-01-13 Simone Anders Monodisperse nanoparticle containing thin films via self-assembly
US6805904B2 (en) 2002-02-20 2004-10-19 International Business Machines Corporation Process of forming a multilayer nanoparticle-containing thin film self-assembly
US20030198021A1 (en) * 2002-04-23 2003-10-23 Freedman Philip D. Structure with heat dissipating device and method to produce a computer
US7208191B2 (en) 2002-04-23 2007-04-24 Freedman Philip D Structure with heat dissipating device and method
US20070122622A1 (en) * 2002-04-23 2007-05-31 Freedman Philip D Electronic module with thermal dissipating surface
US7879260B2 (en) 2002-10-04 2011-02-01 Mitsubishi Chemical Corporation Additive for anode material for lithium secondary battery, anode material for lithium secondary battery, anode and lithium secondary battery using the anode material for lithium secondary battery
US20050221184A1 (en) * 2002-10-04 2005-10-06 Mitsubishi Chemical Corporation Additive for anode material for lithium secondary battery, anode material for lithium secondary battery, anode and lithium secondary battery using the anode material for lithium secondary battery
EP1548862A4 (en) * 2002-10-04 2009-04-22 Mitsubishi Chem Corp MATERIAL AND ADDITIVE FOR LITHIUM ACCUMULATOR CATHODE MATERIAL, CORRESPONDING USES, CATHODE AND LITHIUM ACCUMULATOR THUS OBTAINED
EP1560282A4 (en) * 2002-10-31 2009-04-29 Mitsubishi Chem Corp POSITIVE ELECTRODE MATERIAL FOR A LITHIUM SECONDARY BATTERY AND POSITIVE ELECTRODE AND LITHIUM SECONDARY BATTERY OBTAINED FROM SUCH MATERIAL
EP2946666A1 (en) 2004-04-30 2015-11-25 OrbusNeich Medical, Inc. Medical device with coating for capturing genetically-altered cells and methods of using same
US7780875B2 (en) * 2005-01-13 2010-08-24 Cinvention Ag Composite materials containing carbon nanoparticles
US20060155376A1 (en) * 2005-01-13 2006-07-13 Blue Membranes Gmbh Composite materials containing carbon nanoparticles
US20060167147A1 (en) * 2005-01-24 2006-07-27 Blue Membranes Gmbh Metal-containing composite materials
US7071047B1 (en) 2005-01-28 2006-07-04 International Business Machines Corporation Method of forming buried isolation regions in semiconductor substrates and semiconductor devices with buried isolation regions
US7352030B2 (en) 2005-01-28 2008-04-01 International Business Machines Corporation Semiconductor devices with buried isolation regions
US20060172479A1 (en) * 2005-01-28 2006-08-03 International Business Machines Corporation Method of forming buried isolation regions in semiconductor substrates and semiconductor devices with buried isolation regions
US7531209B2 (en) 2005-02-24 2009-05-12 Michael Raymond Ayers Porous films and bodies with enhanced mechanical strength
US8034890B2 (en) 2005-02-24 2011-10-11 Roskilde Semiconductor Llc Porous films and bodies with enhanced mechanical strength
US20090192281A1 (en) * 2005-02-24 2009-07-30 Michael Raymond Ayers Porous Films and Bodies with Enhanced Mechanical Strength
US20060185794A1 (en) * 2005-02-24 2006-08-24 Ayers Michael Raymond Porous films and bodies with enhanced mechanical strength
US20060228828A1 (en) * 2005-04-11 2006-10-12 Miller Seth A Versatile system for selective organic structure production
US20070003749A1 (en) * 2005-07-01 2007-01-04 Soheil Asgari Process for production of porous reticulated composite materials
US7875315B2 (en) * 2006-05-31 2011-01-25 Roskilde Semiconductor Llc Porous inorganic solids for use as low dielectric constant materials
US7883742B2 (en) 2006-05-31 2011-02-08 Roskilde Semiconductor Llc Porous materials derived from polymer composites
US7919188B2 (en) * 2006-05-31 2011-04-05 Roskilde Semiconductor Llc Linked periodic networks of alternating carbon and inorganic clusters for use as low dielectric constant materials
US7790234B2 (en) 2006-05-31 2010-09-07 Michael Raymond Ayers Low dielectric constant materials prepared from soluble fullerene clusters
US20080020197A1 (en) * 2006-05-31 2008-01-24 Roskilde Semiconductor Llc Porous inorganic solids for use as low dielectric constant materials
WO2007143026A3 (en) * 2006-05-31 2008-02-28 Michael Raymond Ayers Linked periodic networks of alternating carbon and inorganic clusters for use as low dielectric constant materials
US20080108774A1 (en) * 2006-05-31 2008-05-08 Roskilde Semiconductor Llc Linked periodic networks of alternating carbon and inorganic clusters for use as low dielectric constant materials
CN112941906A (en) * 2021-03-03 2021-06-11 厦门福纳新材料科技有限公司 Fullerene composite fiber fabric and preparation method thereof
CN115845638A (en) * 2022-11-24 2023-03-28 河海大学 Modified polyvinylidene fluoride composite membrane for membrane distillation and preparation method thereof

Similar Documents

Publication Publication Date Title
US5338571A (en) Method of forming self-assembled, mono- and multi-layer fullerene film and coated substrates produced thereby
Van de Mark et al. A poly-p-nitrostyrene electrode surface. Potential dependent conductivity and electrocatalytic properties
Gardner et al. Systems for orthogonal self-assembly of electroactive monolayers on Au and ITO: an approach to molecular electronics
Nyokong Electronic spectral and electrochemical behavior of near infrared absorbing metallophthalocyanines
Kondo et al. Adsorption behavior of functionalized ferrocenylalkane thiols and disulfide onto Au and ITO and electrochemical properties of modified electrodes: Effects of acyl and alkyl groups attached to the ferrocene ring
Uosaki et al. Electrochemical characteristics of a gold electrode modified with a self-assembled monolayer of ferrocenylalkanethiols
Li et al. Multibit memory using self‐assembly of mixed ferrocene/porphyrin monolayers on silicon
Bilewicz et al. Monomolecular Langmuir-Blodgett films at electrodes. Formation of passivating monolayers and incorporation of electroactive reagents
Sun et al. Selective electrostatic binding of ions by monolayers of mercaptan derivatives adsorbed to gold substrates
Seo et al. A molecular approach to an electrocatalytic hydrogen evolution reaction on single-layer graphene
Benedetto et al. Electro-reduction of diazonium salts on gold: Why do we observe multi-peaks?
Ozoemena et al. Insights into the surface and redox properties of single-walled carbon nanotube—cobalt (II) tetra-aminophthalocyanine self-assembled on gold electrode
Xu et al. The chemistry of self-assembled long-chain alkanethiol monolayers on gold
Sheridan et al. Covalent attachment of porphyrins and ferrocenes to electrode surfaces through direct anodic oxidation of terminal ethynyl groups.
Sinapi et al. Self-assembly of (3-mercaptopropyl) trimethoxysilane on polycrystalline zinc substrates towards corrosion protection
Chen et al. A Molecule with Dual Functionality 4‐Aminophenylmethylphosphonic Acid: A Comparison Between Layers Formed on Indium Tin Oxide by In Situ Generation of an Aryl Diazonium Salt or by Self‐Assembly of the Phosphonic Acid
US6818117B2 (en) Electrochemically directed self-assembly of monolayers on metal
Horikoshi et al. Synthesis, redox behavior and electrodeposition of biferrocene-modified gold clusters
Bilewicz et al. Monomolecular Langmuir-Blodgett Films at Electrodes. Electrochemistry at Single Molecule" Gate Sites"
Uosaki et al. Electron and ion transfer through multilayers of gold nanoclusters covered by self-assembled monolayers of alkylthiols with various functional groups
JPH043907A (en) Capacitor and its manufacturing method
Brito et al. Chemical derivatization of self-assembled 3-mercaptopropionic and 16-mercaptohexadecanoic acids at platinum surfaces with 3-aminopropyltrimethoxysilane: a spectroscopic and electrochemical study
Ikeda et al. Ferrocene on insulator: silane coupling to a SiO2 surface and influence on electrical transport at a buried interface with an organic semiconductor layer
Oyama et al. Spontaneous coating of graphite electrodes by amino ferrocenes
Akiyama et al. Preparation of Molecular Assemblies of Porphyrin-Linked Alkanethiol on Gold Surface and Their Redox Properties.

Legal Events

Date Code Title Description
AS Assignment

Owner name: NORTHWESTERN UNIVERSITY, ILLINOIS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:MIRKIN, CHAD A.;CHEN, KAIMIN;CALDWELL, W. BRETT;REEL/FRAME:006479/0430

Effective date: 19930318

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20060816